Epoxyoxazolidinones



Patented Dec. 10, 1968 3,415,901 EPOXYOXAZOLIDINONES Charles H. Schramm, Easton, Pa., and Claude J. Schmidle,

Hudson, Ohio, assignors to J. T. Baker Chemical Company, Phillipsburg, N.J., a corporation of New Jersey No Drawing. Original application Dec. 20, 1965, Ser. No. 515,149. Divided and this application Sept. 20, 1967, Ser. No. 679,276

10 Claims. (Cl. 260--830) ABSTRACT OF THE DISCLOSURE Polymerizable and polymerized compositions of: (A) an epoxyoxazolidinone of the formula H at- O .1 N C LZ MQQCH...

J LL i L wherein Z is the organic residue of an organic polyisocyanate; Z is the organic residue of a poly(halohydrin); m is an integer of 1 to 5 and n is an integer of 2 to and (B) a polymerization catalyst or epoxy reactive comonomer.

This application is a division of application Ser. No. 515,149 filed Dec. 20, 1965, said application being a continuation-in-part of our copending application Ser. No. 274,923, filed on Apr. 23, 1963.

This invention relates to a novel class of epoxyoxazolidinone derivatives and to a method for their preparation. In a particular aspect this invention relates to polymerizable and polymerized 2-oxazolidinone compounds having at least one epoxy-containing substituent and to intermediates for their preparation. The polymers of the present invention range from elastic and fiberforming thermoplastic resins to hard, tough thermoset resins.

It is an object of the present invention to provide a method for producing epoxyoxazolidinone derivatives.

It is another object of this invention to provide polymeriza-ble; polymerized, and copolymerized epoxyoxazolidinone compositions.

It is another object of this invention to provide resins uniquely adapted for many of the same applications as polyurethane resins.

It is a further object of the present invention to provide novel epoxy resins having improved properties as compared to conventional epoxy resins.

Other objects and advantages of the present invention will become apparent to one skilled in the art from the accompanying description and disclosure.

Accordingly, one or more of the objects of the present invention can be accomplished by a process which comprises subjecting a poly(beta-haloalkylurethano) halohydrin to dehydrohalogenation conditions to produce a poly(epoxyalkyl-Z-oxazolidinone) compound containing at least one 2-oxazolidinone group and at least two epoxy groups.

Poly('beta-haloalkylurethano) halohydrin can be prepared by the reaction of a polyisocyanate with a poly- (halohydrin) in quantities providing between about 1.1 and 4.0 halohydrin groups per isocyanato group.

The term polyisocyanate refers to compounds containing two or more isocyanato (--NCO) groups.

The term poly(halohydrin) refers to compounds containing two or more halohydrin groups, wherein X is halogen.

The term beta-haloalkylurethano refers to the X (-NH-COr-O--Q radical.

The term epoxide or epoxy refers to the oxirane group G C I The term 2-oxazolidinone refers to the structure:

/C=O C-N The term epoxyoxazolidinone or epoxy-substituted 2-oxazolidinone refers to organic compounds containing one or more Z-oxazolidinone groups and one or more epoxy groups and which are generally characterized by an average molecular weight up to about 5,000 and higher.

The term poly(epoxyalkyl-Z-oxazolidinone) refers to organic compounds containing one or more 2-oxazolidinone groups and two or more epoxy groups.

The preparation of ('beta-haloalkylurethano) halohydrin compounds and poly(beta-haloalkylurethano) halohydrin compounds is more fully described in our copending patent application Ser. No. 515,150, filed on Dec. 20, 1965. A preferred class of poly(beta-haloalkylurethano) halohydrin compounds can be represented by the formula:

wherein Z is a polyvalent organic radical selected from aliphatic and aromatic structures such as alkylene, substituted alkylene, alkyleneoxy, alkenylene, substituted alkenylene, arylene, substituted arylene, and the like; Z is a polyvalent organic radical selected from aliphatic and aromatic structures such as alkylene, substituted alkylene, alkyleneoxy, cycloalkylene, substituted cycloalkylene, arylene, substituted arylene, aryleneoxy, aralkylene, substituted aralkylene, and the like; and Z can also be zero, i.e., Z can be a covalent bond directly connecting two halohydrin moieties; X is halogen, preferably chlorine or bromine; m is an integer between 1 and 5, and n is an integer between 2 and 10. Particularly preferred compounds corresponding to the above general formula for the poly(beta-haloalkylurethano) halohydrin compounds are those having a molecular weight up to about 5,000 and higher.

Within the above illustrated class of poly(beta-haloalkylurethano) halohydrin compounds, those represented by the following formula are particularly preferred:

HnX

wherein Z, X, Z, in and n have the same meaning given in the above illustrated formula for the poly(beta-ha1oalkylurethano) halohydrin compounds. Preferably Z is tolylene; X is chlorine or bromine and particularly chlorine; mis 1; n is 2; and Z is selected from the group consisting of alkylene, e.g., methylene, ethylene, propylene, etc.; chlorine substituted alkylene, e.g., divalent chloroethylene, and alkyleneoxy, e.g., methyleneoxy, ethyleneoxy, propyleneoxy, and the like. Illustrative of a Z group is the organic residue of a dihalohydrin prepared by reacting epichlorohydrin with a poly(oxyalkylene) glycol having from 2 to 4 carbon atoms in each alkylene group. The epichlorohydrin reacted with the poly(oxyalkylene) glycol is preferably in a molar ratio of 2 moles of epichlorohydrin per mole of poly(oxyalkylene) glycol. This organic residue can be represented by the formula:

wherein R is alkylene of 2 to 4 carbon atoms and n represents repeating units of the (OR) groups. The molecular weight of the poly(oxyalkylene) glycol reactant for the preparation of the polyhalohydrin can vary over a broad range from about 100 to 4,000 and preferably from about 150 to 1,000. The integer n for the (OR) groups will have the same value as the number of repeating (OR) groups of the poly(oxyalkylene) glycol reactant.

Illustrative of the above described process for the preparation of an epoxyoxazolidinone is the interaction of hexamethylene diisocyanate with 2,3-dichloro-1,4-butanediol followed by dehydrochlorination to produce 1,6- bis(4-epoxy-2oxazolidinon-3-yl)hexane:

our-oH-CHN crr2).;-N-C-0HCH Formula C Epoxyoxazolidinone derivatives contemplated to be produced by the invention process include those which correspond to the structure:

Among the preferred epoxyoxazolidinone derivatives are those which correspond to the structure:

Formula A wherein Z is a polyvalent orgaic radical selected from aliphatic and aromatic structures such as alkylene, substituted alkylene, alkyleneoxy, alkenylene, substituted alkenylene, arylene, substituted arylene, and the like; Z is a polyvalent organic radical selected from aliphatic and aromatic structures such as alkylene, substituted alkylene, alkyleneoxy, cycloalkylene, substituted cycloalkylene, arylene, substituted arylene, aryleneoxy, aralkylene, substituted aralkylene, and the like, and Z can also be zero, i.e., Z can be a covalent bond directly connecting an oxazolidinone group with an epoxy group; G is sulfur or oxygen and preferably oxygen, In is a whole number of from 1 to 5 and higher, and n is a whole number of from 2 to and higher. Preferably, Z is tolylene and n is 2. In another aspect of this invention described more fully hereinafter, the compounds can contain a single epoxy group, ie., in the above general formula, in and are equal to one.

Within the above illustrated class of epoxyoxazolidinone derivatives, those represented by the following formula are particularly preferred:

Formula B wherein Z, Z, In and n have the same meaning as in the above illustrated class of epoxyoxazolidinones. Preferably, Z is tolylene or another divalent hydrocarbon group having from about 6 to 12 carbon atoms, e.g., alkylene, alkphenylene, phenylene, etc.; m is I; n is 2; and Z is selected from the groups consisting of alkylene, e.g., methylene, ethylene, propylene, etc.; chloro-substituted alkylene, e.g., divalent chloroethylene; and alkyleneoxy, e.g., methyleneoxy, ethyleneoxy, propyleneoxy and the like. Illustrative of a Z' group is the orgaic residue of a dichlorohydrin prepared by reacting epichlorohydrin with a poly(oxyalkylene) glycol having from 2 to 4 carbon atoms in each alkylene group. Preferably, the epichlorohydrin is reacted with the poly(oxyalkylene) glycol in a molar ratio of 2 moles of epichlorohydrin per mole of poly(oxyalkylene) glycol. This organic residue can be represented by the formula:

wherein R is alkylene of 2 to 4 carbon atoms and n represents repeating units of the (OR) group.

In addition to carbon, hydrogen, oxygen, sulfur, nitrogen and halogen atoms, the compounds and resins of the present invention can contain silicon, titanium, phosphorus, and the like.

Isothiocyanate reactants are also suitable in lace of the isocyanates. Polyisocyanate and polyisothiocyanate reactants suitable for use in the production of the present invention epoxyoxazolidinones (also referred to herein as epoxyoxazolidones) include isocyanato compounds and prepolymers which are being developed for commercially important polyurethane chemistry. Among the preferred polyisocyanates and polyisothiocyanates are those corresponding to the formula R(NCG) wherein G is oxygen or sulfur, x is an integer of two or more, and R is an alkylene, substituted alkylene, arylene or substituted arylene radical, a hydrocarbon or substituted hydrocarbon containing one or more aryl NCG bonds and one or more alkyl NCG bonds. R can also include radicals such as RZR where Z can be a divalent moiety such as O, -ORO, -CO-, CO S, SRS, SO and the like. Examples of such compounds include hexamethylene diisocyanate, xylylene diisocyanates, (OCNCH CH CH OCH 1-methyl-2,4- diisocyanatocyclohexane, phenylene diisocyanates, tolylene diisocyanates, chlorophenylene diisocyanates, polyhalophenylene diisocyanate, diphenylmethane-4,4-diiso cyanate, naphthalene-1,5-diisocyanate, triphenylmethane- 4,4,4-triisocyanate, xylene-aux-diisothiocyanate, and isopropylbenzene-a,4-diisocyanate.

Further included are dimers and trimers of isocyanates and diisocyanates and polymeric diisocyanates of the general formula (RNCG) and [R(NCG) in which x and y are two or more, as well as compounds of the general formula M(NCG) in which x is two or more and M is a monofunctional or polyfunctional atom or group. Examples of this type include ethylphosphonic diisocyanate, C H P(O) (NCO) phenylphosphoric diisocyanate, C H PO(NCO) compounds containing a =SiR(SO NCO) and the like.

A particularly useful mixture of polyisocyanates are the products obtainable by phosgenation of the reaction products of aniline and formaldehyde as expressed by the following general formula:

I IITC O lfoo l- NCO on, CH2- |l1 wherein n=0 to 10.

wherein m is an integer between 2 and 5, and X and Z are defined hereinabove. X is preferably chlorine or bromine.

Poly(halohydrin) compounds are readily produced by hydrohalogenation of the corresponding polyepoxide compounds. For example, treatment of divinylbenzene dioxide with hydrogen chloride yields the corresponding poly(halohydrin) structure:

Useful poly(halohydrin) compounds include 1,4-dichlorobutanediol-2,3, 1,4-dibromobutanediol-2,3, 2,3-dichlorobutanediol-1,4, 2,3-dibromobutanediol-1,4, vinylcyclohexene dichlorohydrin, 3,3 dichloro 2,2'-dihydroxydipropylether, epichlorohydrin adducts of polyols and polyhydric phenols including l,2-ethylenedioxy-bis- (3-chloro-2-propanol), 1,4-butylenedioxy-bis (3-chloro- 2-propanol), and the like, and the corresponding epichlorohydrin adducts of other such polyols such as polyethylene glycol, polypropylene glycol, polybutylene glycol,

mixtures of said poly(oxyalkylene) glycols, resorcinol,

glycerol, pcntaerythritol, sorbitol, poly(vinyl alcohol), and the like.

Other useful poly(halohydrin) compounds are the halohydrin compounds which correspond to polyepoxides (wherein each oxirane group is instead a halohydrin group) such as aliphatic polyol epoxycyclohexanecan boxylates exemplified by compounds which include 3-methyl-1,5-pentanediol bis(3,4-epoxycyclohexanecarboxylate 1,5-pentanediol bis(3,4-epoxycyclohexanecarboxylate) 2-methoxymethyl-2,4-dimethyl-1,5-pentanediol bis 3,4-epoxycyclohexanecarboxylate) ethylene glycol bis(3,4-epoxycyclohexanecarboxylate) 2,2-diethyl-1,3-propanediol bis(3,4-epoxycyclohexanecarboxylate 1,6-hexanediol bis( 3,4-epoxycyclohexanecarboxylate) 2butenel ,4-diol bis (3 ,4-epoxycyclohexanecarboxylate 2-butene-1,4-diol bis(3,4-epoxy-6-methylcyclohexanecarboxylate) 1,2,3-propanetriol tris(3,4-epoxycyclohexanecarboxylate) oxyalkylene glycol epoxycyclohexanecarboxylate exemplified by compounds which include dipropylene glycol bis(2-ethylhexyl-4,S-epoxycyclohexane-1,2-dicarboxylate) diethylene glycol bis(3,4-epoxy-6-methylcyclohexanecarboxylate), triethylene glycol bis(3,4-epoxycyclohexanecarboxylate); epoxycyclohexylalkyl epoxycyclohexaneboxylates exemplified by compounds which include 3,4-epoxycyclohexylmethyl 3,4-epoxycyclohexanecarboxylate, 3,4-epoxy-l-methylcyclohexylmethyl 3,4-epoxy-lmethylcyclohexanecarboxylate, 3 ,4-epoxy-2-methylcyclohexylmethyl 3,4-epoxy-2- methylcyclohexanecarb oxylate, (1-chloro-3,4-epoxycyclohexan-1-yl)methyl l-chloro- 3,4-epoxycyclohexanecarboxylate, (l-brorno-3,4-epoxycyclohexan-l-yl)rnethy1 l-bromo- 3,4-epoxycyclohexanecarboxylate, (l-chloro-2-1nethyl-4,S-epoxycyclohexan-l-yl) methyl l-chloro-2-methyl-4,5-epoxycyclol1exanecarboxylate; epoxycyclohexylalkyl dicarboxylates exemplified by compounds which include bis(3,4-epoxycyclohexylmethyl) pimelate, bis(3,4-epoxy-6-methylcyclohexylrnethyl) maleate, bis(3,4-epoxy-6-methylcyclohexylmethyl) succinatc, bis(3,4-epoxycyclohexylmethyl) oxalate, bis(3,4-epoxy-6-methylcyclohexylmethyl) sebacate, bis(3,4-epoxy-6-rnethylcyclohexylmethyl) adipate; epoxycyclohexylalkyl phenylenedicarboxylates exemplified by compounds which include bis(3,4-epoxycyclohexylmethyl) terephthalate, bis(3,4-epoxy-6-methylcyclohexylmethyl) terephthalate; epoxycyclohexylalkyl oxyalkylene glycol ethers exemplified by compounds which include bis (3 ,4-epoxy-6-methylcyclohexylmethyl) dliethylene glycol ether; sulfonyldialkanol bis(epoxycyclohexanecarboxylates) exemplified by compounds which include 2,2-sulfonyldiethanol bis 3 ,4-epoxycyclohexanecarboxylate); epoxycyclohexane-1,2-dicarboximides exemplified by compounds which include N,N-ethylene bis(4,5-epoxycyclohexane-1,2-

dicarboxirnide) epoxycyclohexylalkyl car bamates exemplified by compounds which include di(3,4-epoxycyclohexylmethyl) 1,3-tolylenedicarbamatc; epoxycyclohexylalkyl acetals exemplified by compounds which include bis(3,4-epoxy-6-methylcyclohexylrnethyl) 3,4-epoxy-6- methylcyclohexanecarboxaldehyde acetal; and epoXyclohexyl-substituted spirobi (metadioxane) derivatives exemplified by compounds which include 3,9-bis(3,4-epoxycyclohexyl)spirobi (metadioxane).

Other poly(halohy.drin) compounds can be employed which correspond to polyepoxide derivatives such as 3,4- epoxy-o-methylcyclohexylmethyl 9,10-epoxystearate, 1,2- bis(2,3-epoxy 2-methylpropoxy)ethane, the diglycidyl ether or 2,2-(p-hydroxylphenyl)propane, butadiene dioxide, dicyclopentadiene dioxide, pentaerythritol tetrakis- (3,4 epoxycyclohexanecarboxylate), divinylbenzene dioxide, and the like.

A preferred class of poly(halohydrin) reactants are those which can be represented by the formula:

wherein R is straight or branched chain alkylene having from 2 to 4 carbon atoms, e.g., propylene, and n represents repeating units of the (OR) group. Such po1'y(halohydrins) can be prepared by the reaction of 2 moles of epichlorohydrin with one mole of a poly(oxyalky1ene) glycol having from 2 to 4 carbon atoms in each alkylene group in the presence of a catalyst such as boron trifluoride etherate. The molecular weight of the poly(oxyalkylene) glycol can vary over a broad range such as that of from about to 4,000 and preferably from 7 about 150 to 1,000. Another preferred class of poly (halohydrin) reactant is poly(epichlorohydrin).

The useful poly(halohydrin) reactants also include those prepared by halohydrination of polyunsaturated compounds which contain two or more olefinically unsaturated groups reactive to hypohalite addition reactions.

The dehydrohalogenation reaction producing epoxyoxazolidinones is readily accomplished by treating poly (beta-haloalkylurethano) halohydrin with an inorganic or organic acid acceptor such as alkali metal hydroxides and carbonates, ion exchange resins, pyridine, amines, and the like. For example, the dehydrohalogenation can be accomplished by heating the poly(beta-haloalkylurethano)halohydrin with aqueous potassium hydroxide at a temperature between C. and 150 C. for a period from about five minutes to about four hours or by heating the product mixture with pyridine either in aqueous medium or an organic solvent medium.

The epoxyoxazolidinone compositions of the present invention characteristically range from highly viscous liquids to rubber-like and hard solids. They can be cured with epoxy curing catalysts or reacted with epoxy hardeners, either alone or with other materials, e.g., epoxy monomers and resins, to yield the broad variety of valuable new polymers provided by the present invention. These polymers have many advantageous properties. The particular properties will of course depend on the particular composition since the polymers range from elastic and fiber-forming thermoplastic resins to hard, tough thermoset resins. Illustrative of advantageous properties there can be mentioned: high elongation, good tensile strength, impact resistance, resistance to tearing, resistance to cracking or breaking by changes in temperature (thermal shock), room temperature curing and solvent resistance. Also, the polymeric compositions of this invention can tolerate fairly large quantities, e.g., 50% to 100% of conventional fillers, e.g., silica powder, alumina, aluminum, etc., without deleteriously affecting the properties of the polymers. The polymers have a wide range of applications and uses such as: adhesives, castings, caulking and sealing compounds, coatings, concrete bonding agents, electrical casting, encapsulant and potting compounds, filament winding, industrial flooring, laminates, molding resins, prepregs and tooling compositions.

The polymerizable epoxyoxazolidinone compositions comprise mixtures of the epoxyoxazolidinone composition described hereinahove and a catalytic quantity of an active polymerization agent. The quantity of catalyst employed can vary in the range between about 0.005 and weight percent based on the total Weight of the polymerizable material in a composition, with between about 0.01 and 10 weight percent being the preferred Weight range. Suitable polymerization catalysts include acids such as sulfuric acid, alkanesulfonic acids, benzenesulfonic acid, perchloric acid, phosphoric acids, and the like; metal halide Lewis acids and their complexes, such as stannic chloride, stannic bromide, ferric chloride, aluminum chloride, zinc chloride, boron trifiuoride, boron trifiuoride-ether complexes, boron trifiuoride amine complexes, e.g., boron trifiuoride-monoethylamino complex, boron trifiuoride-piperidine complex, and the like; bases such as sodium hydroxide, alkali metal alcoholates, tertiary amines, e.g., benzyldimethylamine, dimethylaminomethylphenol, triethylenediamine, 2,4,6 tri(dimethylaminomethyl)phenol, and the like; alkyl titanates such as tetraisopropyl titanate, tetrabutyl titanate, and the like; and other similar catalysts having curing activity. The particularly preferred catalysts from this group include stannic chloride, stannic bromide, boron trifiuorideetherate, boron trifiuoride-amine complexes, metal fluoborates, e.g., zinc fiuorborate, copper fluoborate, lead fluoborate, and tetraalkyl titanates, e.g., tetraisopropyl titanate, and tetrabutyl titanate.

The polymerizable compositions comprising an epoxyoxazolidinone and a polymerization cataylst can be prepared by the simple expediency of mixing together the composition components at room temperature. The polymerizable compositions can be prepared at the time that they are to be utilized or they can be prepared and stored for future application. The incorporation of the catalyst into the polymerizable compositions can be facilitated if desired, by preparing a catalyst solution with a suitable solvent such as xylene, "ethyl acetate, heptane, dioxane, ethyl ether, and the like. Small quantities of water can be used as a solvent with most of the catalysts with the exception of those which decompose in water, e.g., aluminum chloride.

The resinous compositions of this invention are readily obtained from the polymerizable compositions by the application of heat. The curing, i.e., polymerization, occurs readily with or without a solvent at a temperature in the range between about 10 C. and 200 C. The polymerization time can vary over a wide range from several minutes to several days depending on such factors as the nature of the epoxyoxazolidinone, the quantity and reactivity of the catalyst, the absence or presence of a solvent, and the like. It is advantageous to perform the polymerization in a solvent or solvent mixture. Suitable solvents include hydrocarbons such as benzene, xylene, toluene, hexane, heptane, octane, cyclohexane, and various terpenes; oxygenated solvents such as acetone, methylisobutylketone, cyclohexanone, ethyl acetate, butyl acetate, amyl acetate, dioxane, tetrahydrofuran, dibutyl ether, and the like; and other common solvents such as carbon tetrachloride, carbon disulfide, and the like. The progress of the polymerization reaction can be observed by determining the relative viscosity of samples drawn from the reaction mixture. In this manner, it is possible to produce partially polymerized compositions or completely polymerized compositions. The presence of solvent permits the maintenance of adequate stirring, and it provides a medium for applying the final resinous material in coatings and other applications.

In another embodiment of this invention, polymerizable compositions having utility in the fields of coating, laminating, bonding, molding, potting, calendering, and the like, can be prepared from the novel epoxyoxaozolidinones by admixing them with various reactive hardening agents. The resinous compositions derived by the polymerization of the admixtures are essentially copolymers of the hardening agent and the epoxyoxazolidinone. The hardening agent, or comonomer, can be any polyfunctional material capable of reaction with epoxide and/ or hydroxyl groups to form polymers having the outstanding properties inherent in the resins of this invention. Such polyfunctional materials include polyepoxides, polycarboxylic acids, polycarboxylic acid anhydrides, polycarboxylic acid halides, polyhydric alcohols and phenols, polythiols, polyisocyanates, polyfunctional amines, polyamides, ureaformaldehyde adducts, melamine-formaldehyde adducts, phenol-formaldehyde adducts, and the like. The resinous compositions are prepared from the polymerizable compositions by the application of heat. Illustrative of useful polymerizable compositions and polymerized resinous copolymer compositions are the following:

1) Polymerizable and polymerized compositions can be prepared from admixtures which comprise (a) epoxyoxazolidinone and (b) a polyfunctional amine, i.e., an amine having at least two active amino hydrogen atoms which can be on the same nitrogen atom or different nitrogen atoms, in an amount sufficient to provide between about 0.2 to 4.0 amino hydrogen atoms per epoxy group of said epoxyoxazolidinone and preferably between about 0.5 to 2.0 amino hydrogen atoms per epoxy group. Suitable polyfunctional amines include monoamines, diamines, triamines, and higher polyamines such as 2-ethylhexylamine, aniline, phenethylamine, cyclohexylamine, Z-aminophenol, l,3-diamino-Z-propanol, etdylenediamine, butylenediamine, xylylenediamine, hexamethylenedi-amine, dihexylenetriamine, diethylenetriamine, triethylenetetraamine, dipropylenetriamine, m-phenylenediamine, p-phenylenediamine, guanidine, p,p'-diaminodiphenylsulfone, p-p'- methylenedianiline, bisaniline-F, aminoethylpiperazine, diethylene triamine, bis(aminopropyl)-piperazine, and the like. The polyfunctional amines can be pre-reacted with epoxy compounds in greater than equivalent proportions to produce modified hardeners with amine end groups. This method permits the use of low-boiling amines which otherwise might be too volatile. Suitable modifier epoxy compounds include ethylene oxide, propylene oxide, butadiene dioxide, soybean oil epoxide, saffiower oil epoxide, 'glyeidyl ethers, and the like. Other suitable modified amine 'hardeners are prepared by the condensation of a polyfunctional amine with an unsaturated compound, e.g., the condensation of diethylenetria-mine with acrylonitrile. Catalysts suitable for polymerizing the admixtures of amines and epoxyoxazolidinones include alcohols, phenols, and metal halide Lewis acid-amine complexes such as piperidine-boron trifluoride, and monoethylamine-boron trifluoride. The catalyst concentration can range from about 0.05 to weight percent based on the total weight of olymerizable components in an admixture. The polymerization reaction can be performed with or without a catalyst, as desired.

(2) Polymerizable and polymerized compositions can be prepared from admixtures which comprise (a) an epoxyoxazolidinone, (b) a polycarboxylic acid in an amount having y carboxyl equivalents of acid per epoxy equivalent of said epoxyoxazolidinone, and (c) a polycarboxylic acid anhydride in an amount having x carboxyl equivalents of anhydride per epoxy equivalent of said epoxyoxazolidinone, where y is a number in the range from about 0.3 to 3.0, x is a number in the range from 0.0 to about 1.5, the sum of y+x is not greater than about 3.0, and x/ y is less than 1.0.

Illustrative polycarboxylic acids which can be employed include aliphatic aromatic, and cycloaliphatic polycarboxylic acids such as oxalic acid, malonic acid, glutaric acid, maleic acid, suberic acid, citraconic acid, 1,2-cyclohexanedicarboxylic acid, phthalic acid, 1,8-naphthalenedicarboxylic acid, 3-carboxycinnamic acid, 1,2,4-butanetricarboxylic acid, l,2,4-hexanetricarboxylic acid, 1,2,4- benzenetricarboxylic acid, and the like; polycarboxy polyesters, i.e., polyesters containing more than one carboxy group per molecule, such as polycarboxylic acids of the type exemplified above, or the corresponding anhydrides, esterified with polyhydric alcohols which include ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, 1,6-hexanecliol, trimethylolpropane, pentaerythritol, dimethylolphenol, inositol, poly (vinyl alcohols), and the like.

Polycarboxylic acid anhydrides which can be employed as modifiers include the anhydrides of maleic acid, chloromaleic acid, dichloromaleic acid, succinic acid, citraconic acid, itaconic acid, alkyl succinic acids, alkenyl succinic acids, phthalic acid, tetrahydrophthalic acid, methyltetrahydrophthalic acid, hexahydrophthalic acid, cholorendic acid, glutaric acid, adipic acid, sebacic acid, and the like It will be noted that the polycarboxylic acid is a major component of the admixture.

Catalysts which are effective in accelerating the curing of the admixtures include acids such as sulfuric, perchloric, polyphosphoric, benzenesulfonic acid, toluenesulfonic acid, and the like. Also included are the metal halide Lewis acids, e.g., boron trifluoride, stannic chloride, zinc chloride, ferric chloride, aluminum chloride and the complexes of these acids, such as boron trifiuoride-ether complex, boron trifiuoride-piperidine complex, boron trifluoride-monoethylamine complex, boron trifluoride-1,6-hexanediamine complex and the like. Catalyst concentrations can vary over the range from 0.001 to 5.0 weight percent based on the weight of polymerizable material.

(3) Polymerizable and polymerized compositions can be prepared from admixtures which comprise (a) an epoxyoxazolidinone, (b) a polycarboxylic acid anhydride in an amount having x carboxyl equivalents of anhydride per epoxy equivalent of said epoxyoxazolidinone, and (c) a modifier compound in an amount having in active hydrogen equivalents of modifier compound per epoxy equivalent of said epoxyoxazolidinone, wherein x is a number in the range from about 0.2 to 4.0, preferably from about 0.5 to 2.0, m is a number in the range from about 0.0 to 1.0, the sum of x+m'is not greater than 4.0 and x/m is at least 1.0. Suitable polycarboxylic acid anhydrides are exemplified by those listed in Section (2) above. The preferred active hydrogen modified compounds are polycarboxylic acids and polyhydric alcohols and phenols. Illustrative of the preferred active hydrogen modifier compounds are ethylene glycol, glycerol, pentaerythritol, inositol, poly(vinyl alcohol), trimethylolphenol, resorcinol, hydroquinone, polyhydric phenolformaldehyde condensation products, oxalic acid, maleic acid, itaconic acid, phthalic acid, 1,1,5-pentanetricarboxylic acid, azelaic acid, malic acid, and the like. Other active hydrogen compounds useful as modifiers can be prepared by the condensation of polyols with dicarboxylic acid anhydrides in such proportions required to give polyesters with carboxyl and hydroxyl end groups. These esters can be prepared from the above-listed anhydrides or acids and polyols such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, propylene glycol, 1,6- hexanediol, glycerol, 1,2,6-hexanetriol, trimethylolpropane, pentaerythritol, trimethylolphenol, inositol, poly- (vinyl alcohol), and the like. Any one or combination of the three types of modifiers can be employed. It will be noted that the polycarboxylic acid anhydride is a major component of the admixtures. Catalysts which are effective in accelerating the anhydride-epoxide reactions of this invention include acids, such as sulfuric acid, perchloric acid, phosphoric acid, polyphosphoric acid, benzenesultonic acid, toluenesulfonic acids, and the like; metal halide Lewis acids, such as boron trifiuoride, stannic chloride, zinc chloride, ferric chloride, aluminum chloride and the complexes of such acids, e.g., boron trifluoride-ether complex, boron trifluoride-piperidine complex, boron trifluoride-monoethylamine complex, boron trifluoride-1,6-hexanediamine complex, and the like; basic catalysts such as the alkali metal hydroxides, e.g., sodium and potassium hydroxides, and amines, e.g., pyridine, alpha-methylbenzyl-dimethylamine, dimethylaminoethylphenol 2,4,6-tris- (dimethylaminomethyl)phenol, triethylamine, trimethylammonium hydroxide, and the like. Catalyst concentrations can vary over the range from 0.001 to 5.0 Weight percent based on the total Weight of olymerizable material.

(4) Polymerizable and'polymerized compositions can be prepared from admixtures comprising (a) an epoxyoxazolidinone and (b) a polyol, i.e., an organic compound having at least tWo hydroxyl groups which are alcoholic hydroxyl groups, phenolic hydroxyl groups, or both alcoholic and phenolic hydroxyl groups, e.g., aliphatic and cycloaliphatic polyalcohols and polyhydric phenols. The polyol is employed in an amount which provides between about 0.2 and 4.0 hydroxyl equivalents per epoxy equivalent of said epoxyoxazolidinone. These compositions can be further modified by incorporating therein a polycarboxylic acid compound or polycarboxylic acid anhydride such as those illustrated in Section (2) above. It is pointed out that the polyol is a major component as compared with the modifier. Typical polyols which can be employed include ethylene glycol, diethylene glycol, glycerol, polypropylene glycols, butanediol, triethanolamine, pentaerythritol, trimethylolethane bis(4-hydroxyphenyl)methane, inositol, sorbitol, trimethylolphenol, resorcinol, pyrogallol, hydroquinone, 1,8-naphthalenediol, 2,4,6-trimethylolphenol allyl ether, cyclohexanediol, and the like.

(5) Polymerizable and polymerized compositions can be prepared from admixtures which comprise (a) an epoxyoxazolidinone and (b) a compound containing two or more epoxide groups in an amount suflicient to provide between 0.2 and 4.0 epoxy equivalents per hydroxyl equivalent of said epoxyoxazolidinone. Suitable epoxides include the diglycidyl ether of bisphenol. A, diglycidyl ether polychlorohydrin and epichlorohydrin adducts of diols and polyols, diglycidyl ether, butadiene dioxide, vinylcyclohexene dioxide, soybean oil epoxide, divinylbenzene dioxide bis(2,3-epoxycyclopentyl) ether, dicyclopentadiene dioxide, the polyepoxides mentioned above from which the poly(halohydrin) reactants of this invention can be prepared, and the like.

(6) Polymerizable and polymerized compositions can be prepared from admixtures Which comprise (a) an epoxyoxazolidinone and (b) a polycarboxylic acid such as those illustrated in Section (2) above in an amount suflicient to provide between 0.3 and 3.0 carboxy-l equivalents per epoxy equivalent of said epoxyoxazolidinone. A polyol of the type exemplified in Section (4) above can be employed to further modify the compositions. In these admixtures the polycarboxylic acid is a major component as compared with the polyol modifier.

(7) Polymerizable and polymerized compositions can be prepared from admixtures comprising (a) an epoxyoxazolidinone and (b) any one of the following classes of compounds, namely, polythiols such as the sulfur analogs of the polyols listed in Section (4) above, phenolaldehyde condensates, urea-aldehyde condensates, melamine-aldehyde condensates, polyamines, polycarboxylic acid halides, and the like.

A preferred class of polymers are those prepared from mixtures of (a) a poly(epoxyalkyl-2-oxazolidinone), e.g., as illustrated in Formula A and Formula B hereinbefore; with (b) a phenolic based polyepoxide such as epichlorohydrin adducts of bisphenol A, i.e., bis(4-hydroxyphenyl)dimethylrnethane, e.g., the diglycidyl ether of hisphenol A; epichlorohydrin adducts of bisphenol F [bis(4- hydroxyphenyl)methane]; and epoxylated novolac resins; and (c) a cross-linking type of curing or hardening agent such as the polyfunctional amines which are mentioned in numbered paragraph (1) of the resinous copolymer compositions or the polycarbox-ylic acid anhydrides mentioned in numbered paragraph (3) of the resinous copolymer compositions. In this preferred class of polymers the ratio, by weight, of poly(epoxyalkyl-2- oxazolidinone) to the phenolic based polyepoxide can vary over a broad range such as that of 10 to 1 and l to 10. Preferably, however, the ratio of these various epoxide reactants varies from about 0.2 to parts of the poly- (epoxyalkyl-2-oxazolidinone) for each part by weight of the phenolic based polyepoxide resin. The curing or hardening agent is preferably employed in about stoichiometric quantities, i.e., a quantity providing one active epoxy reactive site, e.g., hydrogen, of the curing agent for each epoxy group, although this can be varied as is customary in the art, e.g., to provide about 0.5 to 2 active sites for each epoxy group. The preferred curing agents are the polyfunctional amines and particularly aminoethylpiperazine. The preferred phenolic based polyepoxides are liquids, including ve-ry viscous sluggish liquids. This preferred class of polymers, when cured with the polyfunctional amines, has many advantageous properties. Illustrative of such advantageous properties there can be mentioned: high elongation, high tensile strength, impact resistance, room temperature cures, resistance to tearing or breaking, good electrical properties, e.g., dielectric constant, dissipation factor, and dielectric strength, resistance to cracking or breaking due to temperature changes, good resistance to various solvents, e.g., water, hexane and alkalies, such as sodium hydroxide.

This invention also contemplates epoxyoxazolidinone compounds which contain only one epoxy group. These compounds can be produced by the dehydrohalogenation of a (beta-haloalkylurethano)halohydrin as illustrated by the following reaction scheme:

OHZ=CHCHQNCO OlCHzCHOHCHOHCHzCl The 3 allyl 5 epoxyethyl 2 oxazolidinone illustrated above is a unique type of compound which can be polymerized either through the epoxy group or the vinyl group. Once the compound is polymerized (e.g., through the vinyl group), the remaining reactive site in the molecule (e.g., the epoxy group) can serve as a cross-linking means to produce a more thermoset resin.

In comparison to epoxyozalidinones prepared by the direct condensation of epoxides and isocyanates, the process of the present invention minimizes many of the side reactions characteristic of epoxide and isocyanate chemistry, such as homopolymerization of the epoxy groups, and carbodiimide formation and trimerization of the isocyanato groups.

The following examples will serve to illustrate specific embodiments of the present invention.

EXAMPLE 1 Poly(epichlorohydrin) (95 grams) having an average molecular weight of 450 was mixed with dioxane (180 grams) and 2,4-tolylene diisocyanate (17.4 grams). Stannous octoate (0.4 milliliter) was added and the mixture was stirred and kept at 25 to 30 C. overnight. The reaction mixture was added dropwise, with efficient agitation, to 240 grams of 10 percent sodium hydroxide solution at to C. and was allowed to stir for one hour. Four hundred grams of water was added and the lower (organic) layer was separated, dissolved in toluene, .and washed lWlth water. The toluene solution was dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo to yield an epoxyoxazolidinone having .a viscosity of 24,000 cps. at 25 C. (Brookfield). The product contained 2.05 percent oxirane oxygen.

EXAMPLE 2 Poly(epichlorohydrin) (189 grams) having an average molecular weight of 900, containing 3.66 percent OH functionality, was mixed with dioxane (180 grams) and 2,4-tolylenediisocyanate 17.4 grams). The mixture was stirred, stannous octoate (0.4 milliliter) was added, and the reaction temperature was maintained at 25 to 30 C. overnight. The reaction mixture was added dropwise with efficient agitation at 70 to 75 C. to 240 grams of 10 percent sodium hydroxide solution and allowed to stir for one hour. Two hundred and sixty grams of water was added and the lower (organic) layer was separated, dissolved in toluene and washed with water. The toluene solution was dried over sodium sulfate, filtered, and concentrated in vacuo yielding a viscous oil which contained 1.44 percent oxirane oxygen and 28.2 percent chlorine.

EXAMPLE 3 Two hundred and forty-two grams of a poly(epichlorohydrin) (242 grams) of an average molecular weight of 1150 was mixed with dioxane (200 grams) and 2,4-tolylene diisocyanate (17.4 grams). The mixture was stirred and 0.4 milliliter of stannous octoate was added. The reaction mixture was kept at 25 to 30 C. overnight and was then added dropwise, with efficient agitation, to 240 grams of 10 percent sodium hydroxide solution at 70 to 75 C. Stirring was continued for one hour. Four hundred grams of "water was added and the lower (organic) layer was separated, dissolved in toluene, and washed with water. The toluene solution was dried over anhydrous sodium sulfate, filtered, and concentrated in vacuo to give an oil having a viscosity of 19,700 cps. at 25 C. (Brook- Prepared according to the procedure described in US. Patent 2,000,709.

13 field). It contained 1.25 percent oxirane oxygen and 27.63 percent chlorine.

Resins 1, 2, and 3 SAMPLE CURING RECIPE [60 C.15 hours] 20% 17.0 g. Epon 828 0.05 M. 80% 68.0 g. Product of Examples 1, 2,

or 3 0.03 M. 3.36 g. Diethylenetriamine 0.16 equiv.

Diglycidyl ether of bisphenol A, sold by Shell Chemical Company.

2 Amino hydrogen.

Resins 1, 2, and 3 curer at 60 C. to give flame-resistant flexible polymers. Flexible, elastomeric resins were ob tained with 2 and 3.

EXAMPLE 4 A mixture of 28 grams of tolylene diisocyanate (80/ 20-2,4/2,6-isomers) and 200 grams of polypropylene glycol having an average molecular weight of 2,000 was heated and maintained at 120 to 130 C. for three hours with stirring. It was then cooled to 25 C. and a solution of 95 grams of isopropylidene bis [l-(p-phenyleneoxy)-3-chloro-2-propanol] in 95 grams of methylene chloride was added. The mixture was stirred, 0.3 milliliter of stannous octoate added, and allowed to stand overnight. It 'was then added, over the course of one hour, to 500 grams of 10 percent aqueous sodium hydroxide solution with efficient stirring at 80 to 90 C. The mixture was stirred for thirty minutes after the addition was completed. The resulting viscous, resinous product was washed with water and dried.

The resinous product was divided into portions and cured using various organic anhydride and amine hardeners.

1 Plus 1 percent dimethylbenzylamine accelerator.

2 Liquid amine; epoxy adduct of diethylenetriamine and Epon 828.

3 Liquid tertiary amine salt.

Two grams of Shell Curing Agent U was thoroughly mixed with 10 grams of the resin of Example 4. The resulting mixture increased in viscosity .as the mixing was continued and was drawn into the form of a continuous fiber. This was allowed to cure at 35 C. for eight hours. A tough, elastic fiber was obtained.

EXAMPLE 5 Tolylene diisocyanate (17 grams) was mixed with 85 grams of methylene chloride and 85 grams of isopropylidene bis-[l-(phenyleneoxy)-3-chloro-2-propanol]. The mixture was stirred until a homogeneous solution was obtained and 0.4 milliliter of stannous octoate was added.

Cooling was required to maintain the temperature below 35 C. The mixture was allowed to stand overnight at 25 to 30 C. It was then added, over a period of one hour,

1 to 600 grams of percent aqueous sodium hydroxide solution with efiicient stirring. The white, solid resin which was obtained and removed by filtration, washed thoroughly with water, and dried.

Ten grams of the solid resin was dissolved in 40 grams of methyl isobutyl ketone. Two grams of Shell Curing Agent U was added and the solution was poured into a sheet of Teflon ot form a film. After evaporation of the solvent, the film was cured at 100 C. for four hours. A hard, glossy film was obtained.

14 EXAMPLE 6 Epichlorohydrin (200 grams) was added slowly with stirring at C. to a mixture of 1.5 grams of boron trifiuoride etherate in 400 grams of polyethylene glycol having an average molecular weight of 400. The addition required thirty minutes and cooling was necessary to maintain the temperature in the range of 60 to C. After the addition was complete, the mixture was stirred and kept at 65 to 70 C. for one hour. One hundred and seventeen grams of the reaction product was mixed with 200 grams of methylene chloride and 105 grams of Multhrathane F-84 (an isocyanate terminated polyether urethane prepolymer containing 6.5 to 7.0 percent NCO).

One milliliter of stannous octoate was added and the mixture was kept at 25 to 30 C. overnight. The resulting product was added dropwise with elficient agitation to 240 grams of 10 percent aqueous sodium hydroxide solution at 70 C. to C. and was allowed to stir for one hour. Four hundred grams of water was added and the lower (organic) layer was separated, washed thoroughly with water, and dried under vacuum. The product contained 1.1 percent oxirane oxygen. It was mixed with 20 percent Epon 828 and cured at 60 C. with diethylenetriamine, aminoethylpiperazine, and Shell Curing Agent U. Diethylenetriamine (at a concentration of 1 amino hydrogen per epoxy group) yielded snappy rubbers. Aminoethylpiperazine curing afforded rubbers having slow recovery.

Chemical resistance tests Cured, rubber-like polymers obtained from the products of (1) Example 2 cured with Shell Curing Agent U and (2) Example 6 cured with diethylenetriamine were compared with a commercial urethane elastomer (3) Seilon UR T (Seiberling Rubber Company) for resistance to hydrolytic degradation. The above samples were heated for sixteen hours at 70 C. with 10 percent hydrochloric acid. Sample (1) was unchanged in appearance, the acid solution was colorless. Sample (2) was unchanged in appearance, the solution turned yellow. Sample (3), the commercial urethane elastomer, showed definite checking and flaking, the solution turned green. Samples of the three materials were heated with 10 percent hydrochloric acid and also with 10 percent aqueous sodium hydroxide solution for eighty-eight hours at 70 C.

Poly(epichlorohydrin) grams) having an average molecular weight of 450, was mixed with methylene chloride (300 grams) and hexamethylene diisocyanate (33.6 grams). One milliliter of a stannous alkanoate catalyst (metal and Thermit T-9 catalyst) was added and the mix ture was stirred and kept at 25 to 30 C. overnight while being protected from atmospheric moisture by means of a drying tube. The reaction mixture was added dropwise, with efficient agitation, to 480 grams of 10 percent aqueous sodium hydroxide solution at 70 to 75 C. and was allowed to stir at this temperature for one hour. Five hundred grams of water was added and the lower (organic) layer was separated, dissolved in toluene, and washed with water. The toluene solution was dried by azeotrope distillation of the water followed by concentration in vacuo to give a viscous liquid. Curing in the presence of 10 percent diethylenetriamine at 60 C. overnight yielded a rubber-like polymer.

EXAMPLE 8 Poly(epichlorohydrin) (190 grams) having an average molecular weight of 450, was mixed with methylene chloride (300 grams) and p,p'-diphenylmethane diisocyanate (50 grams). One milliliter of stannous octoate was added and the mixture was stirred and kept at 25 to 30 C. overnight under a dry atmosphere. The reaction mixture was then added dropwise, with efficient agitation, to 480 grams of percent aqueous sodium hydroxide solution at 70 to 75 C. and was allowed to stir at this temperature for one hour. Five hundred grams of water was added and the lower (organic) layer was separated, dissolved in toluene, and washed with water. The toluene solution was dried and concentrated in vacuo to give a viscous liquid. Curing with 10 percent diethylenetriamine at 60 C. overnight yielded a flexible polymeric material.

EXAMPLE 9 One milliliter of boron trifluoride-etherate was mixed with trimethylolpropane (45 grams) at a temperature of 65 C. Epichlorohydrin (200 grams) was added dropwise with stirring and with cooling to maintain the temperature in the range of 60 to 65 C. The mixture was stirred for one hour after the addition was complete.

Tolylene diisocyanate (18 grams) was added to a solution of polypropylene glycol (200 grams, approximate molecular weight of 2,000) in 150 grams of methylene chloride and 1.5 milliliters of dibutyltin dilaurate was added. The mixture was stirred and allowed to stand for two hours while being protected from atmospheric moisture.

Seventy-five grains of the epichlorohydrin adduct (6/ 1) of trimethylolpropane was added to the isocyanate polyurethane prepolymer and the mixture was stirred and allowed to stand for sixteen hours.

The reaction mixture was then added dropwise with vigorous agitation to 600 grams of 10 percent aqueous sodium hydroxide solution at a temperature of 65 to 7 0 C. over a period of one hour. After the addition was completed, the mixture was stirred at 65 to 70 C. for an additional forty-five minutes. The aqueous layer was separated and the viscous residue was washed with water, dissolved in methylene chloride and washed with water containing dissolved CO until the pH of the wash water had dropped to 8.0. The methylene chloride solution was dried over anhydrous sodium sulfate, and distilled in vacuo to remove methylene chloride. The viscous, yellow epoxyoxazolidinone which was obtained weighed 145 grams and had an oxirane oxygen content of 1.80 percent.

Curing of the epoxyoxazolidinone Twenty grams of the epoxyoxazolidinone prepared above was mixed with 5 grams of methylnadic anhydride (National Aniline Division, Allied Chemical and Dye Corporation) and 6 drops of benzyldimethylamine. The mixture was cured at 100 C. for two hours to yield a rubbery material having a Shore Durometer A hardness of 60.

Epoxyoxazolidinone as a plasticizer for commercial epoxy resins.

The epoxyoxazolidinones have further use as crosslinking agents for acrylic and other polymers containing reactive groups such as SH, -OH, --COOH, anhydrides or amines to impart toughness, solvent resistance and abrasion resistance to films and coatings. For example, a styrene/alkyl acrylate/methacrylic acid polymer or a styrene/butadiene/acrylic acid polymer or a vinyl acetate/ acrylic acid ploymer are readily cross-linked with the invention poly(epoxyalkyl-Z-oxazolidinone) to impart properties which qualify the resins for application as film forming protective coatings. The invention poly(epoxyalkyl-2-oxazolidinone) compounds can be advantageously incorporated as a component in latex paints.

EXAMPLE 10 Twelve grams of phenylisocyanate was mixed with 41.5 grams of isopropylidene his [1-(p-phenyleneoxy)-3- chloro-Z-propanol], 41.5 grams of methylene chloride and 0.5 cc. of stannous octoate. The mixture was allowed to stand for sixteen hours at room temperature.

Over a period of one hour, the resulting solution was added to a mixture of 30 grams of sodium hydroxide (97.8 percent pellets) in 300 grams of dioxane at 70 to C. with stirring. Stirring was continued for an additional onehour period. The reaction mixture was cooled, neutralized with carbon dioxide and filtered. The filtrate was distilled to dryness in vacuo. The epoxyoxazolidinone product was obtained in the form of a viscous, yellow syrup.

EXAMPLE 11 Dioxazolidone diepoxide from polyethylene glycol 200 Polyethylene glycol having a molecular weight of 200 (400 g.) and boron trifluoride etherate (0.5 ml.) were placed in a 1000 ml. 3-neck flask; controlling the tem perature of the reaction at C. added epichlorohydrin (372 g.) dropwise. After the addition was complete and no further exotherm developed the temperature was raised to C. for 30 minutes. The excess catalyst was neutralized with calcium oxide (12 g.).

Analysis of the dichlorohydrin: Theory-Cl, 18.3%;

OH, 8.8%. FoundCl, 17.95%; OH, 9.12%.

To the above dichloro'hydrin (385 g.) was added dichloroethane (300 ml.) and stannous octoate catalyst (0.5 ml.) in a 1000 ml. 3-neck flask; with stirring, added tolylene diisocyanate (2,42,6) (78.3 g.), controlling the temperature between 5-10 C. for 3 hours and then allowing the temperature to climb to room temperature overnight. The di(beta-haloalkylurethano)dihalohydrin thus formed was then treated with sodium hydroxide (88 g.). The reaction temperature was controlled at 70 C. and allowed to run with vigorous stirring for 2 /2 hours at which time it was cooled and the excess alkali neutralized with carbon dioxide. The solids were filtered off and the filtrate of dioxazolidinone diepoxide was concentrated to a syrup having the following properties:

Elongation (per- Elongation (per- Elongation (per- Elongation (per- Elongation (per- Elongation (per- EXAMPLE 12 Dioxazolidone diepoxide from polypropylene glycol 200 Example 11 is followed with the exception that in place of polyethylene glycol 200, an equal molar amount of polypropylene glycol 200 is employed. The :dioxazolidinone diepoxide thus formed had the following properties:

17 Analysis: Theory-Cl, 0.0%; Oxirane, 4.0%. FoundCl,

3.5%; Oxirane, 3.75%. Viscosity: 11,400 cps. at 25 C. Physical properties: Blend as in Example 11 (i.e., parts, :by weight, of dioxazolidone diepoxide to Epon 828). Cure Cyc1e.--1 week at 22 C.:

3/1 ratio: Tensile (p.s.i.) 3150; Elongation (percent) 164 2/1 ratio: Tensile (p.s.i.) 4450; Elongation (percent) 94 Cure Cycle.-1 week at 105 C.:

3/1 ratio: Tensile (p.s.i.) 4300; Elongation (percent) 27 2/1 ratio: Tensile (p.s.i.) 3500; Elongation (percent) 8 EXAMPLE 13 Dioxazolidone diepoxide from polypropylene glycol 710 (ml. wt. 775) Example 11 is followed with the exception that in place of polyethylene glycol 200, an equal molar amount of polypropylene glycol 710 is employed. The dioxazolidone diepoxide had the following properties:

Viscosity: 1.400 cps. at 25 C.

EXAMPLE 14 Dioxazolidone diepoxide from polypropylene glycol 1010 (ml. wt. 950) EXAMPLE 15 Dioxazolidone diepoxide from hexane 1,6-diol Example 11 is followed with the exception that in place of polyethylene glycol 200, an equal molar amount of hexane 1,6-diol is employed. The dioxazolidone diopoxide thus formed had the following properties: Analysis: Thery--Cl, 0.0%; Oxirane, 5.36%. Found Cl, 4.38%; Oxirane, 3.98%

EXAMPLE 16 Dichlorohydrin from poly(oxypropylene) clycol and epichlorohydrin Polypropylene glycol 300 (293 g.) and boron trifiuoride etherate (0.5 ml.) were placed in a 3-neck roundbottom flask. Controlling the temperature of reaction between 78 80" C. added slowly, epichlorohydrin 194.2 g.). After addition was completed the temperature was raised to 90 C. for 30 minutes. The excess catalyst was neutralized with calcium oxide (6 g.). The analysis of the dichlorohydrin thus formed was as follows:

Analysis: Theory-Cl, 14.5%; OH, 7.2%.

Cl, 15.4%; OH, 6.81%

EXAMPLE 17 'Di(,B-chloromethylurethano) dichlorohydrin (A) The dichlorohydrin of Example 16 (129 g.), dichloroethane (130 ml.) and stannous octoate catalyst (0.1 ml.) were placed in a 3-neck round-bottom flask. With stirring, added tolylene diisocyanate (2,42,6)

Found 18 (19.14 g.) controlling the temperature between 5-10 C. The temperature was allowed to come to room temperature overnight. The di(fl-chloromethylurethona) dichlorohydrin thus formed had the following properties: Analysis: Theory-Cl, 12.9%; OH, 5.8%. Found- Cl, 13.9%; 0H, 5.38%

Viscosity: 3,750 cps. at 25 C.

(B) The dichlorohydrin (Example 16) 129 g.) and tolylene diisocyanate (2,42,6) (19.14 g.) were placed in a 3-neck round-bottom flask and with stirring, heated at C. for 5 hours. The di(fl-chloromethylurethano) dichlorohydrin thus formed had the following properties: Analysis: Found-Cl, 13%; OH, 3.57%; N, 2.54%

EXAMPLE 18 Dioxazolidone diepoxide (A) To the di(fi-chloromethylurethano) dichlorohydrin [Example 17 (A)] in dichloroethane was added sodium hydroxide. The temperature was controlled between 70-80" C. and allowed to stir for 2 hours, at which time the mixture was cooled and the excess alkali neutralized with carbon dioxide. The solids were filtered off and the filtrate concentrated to an amber syrup of the dioxazolidone diepoxide having the following properties:

Analysis: Found-Cl, 2.6%; Oxirane, 3.5%. Viscosity: 4,070 cps. at 25 C. 114868 Physical properties: Blend as in Example 11 Cure cycle1 week at 22 C., ratio:

Tensile (p.s.i.) 2,800 Elongation (Percent) 1 62.5 Shore D, 50 Water Resistance, 10.3% Electrical:

Capacitance 1 kc., 1 6.75 100 kc., 14.38 Dielectric constant 1 kc., 4.13 100 kc., 3.54 Dissipation Factor 1 kc., 0.046 100 kc., 0. 040 Cure cycle-4 week at 0., 3' ratio:

Tensile (p.s.i.) 4350 Elongation (Percent) Shore D, 67 Water Resistance, 16.1%

Electrical:

Capacitance 1 kc., 15.84 100 kc., 14.18 Dielectric constant 1 kc., 3.94 100 kc., 3.52 Dissipation Factor '1 kc., 0. 032 100 kc., 0.028 (B) The di(fl-chlorornethylurethano) dichlorohydrin [Example 17(B)] in dichlorohydrin was treated the same as in Example 18(A). It had the following properties: Analysis: FoundCl, 2.94%; Oxirane, 3.5% Viscosity: 4,340 cps. at 25 C.; 1.4870 Physical properties: Blend as in Example 11 Cure cycle-1 week at 22 C., ratio:

Tensile (p.s.i.) 3300 Elongation (Percent) Shore D, 55 Water Resistance, 13.2% Electrical:

Capacitance 1 kc., 17.73 100 kc., 15.59

19 Dielectric constant 1 kc., 4.02 100 kc., 3.53 Dissipation Factor 1 kc., 0.034 100 kc., 0.038 Cure cycle-1 week at 105 C., ratio:

Tensile (p.s.i.) 3850 20 1/1 ratio:

Tensile (p.s.i.) 3150 Elongation (percent) 55 Shore D, 59 Cure Cyclel week at 105 C.

3/1 ratio:

Tensile (p.s.i.) 640 Elongation (percent) 82 Elongation (Percent) 106.5 /?hl' D, 22 Shore D 72 2 a ll) Water resistance, 18.1% Tensile (p.s.l.) 2000 Electrical: Elongation (percent) 89 Capacitance wi 36 1 kc., 1 6.17 r 100 k 1455 Tensile (p.s.i.) 4200 Dielectric constant Elonga (P 27 1 kc., 3.86 Shore D, 70 100 kc., 3.48 EXAMPLE t' F t Dlsslpa Ion or Dioxazolidone tetra-epoxide from triol 4542 1 kc, 0.027 20 1 0 kc 0 02 ca. 4500) EXAMPLE 19 TllOl 4542 3 (1125 g.) (0.25 M) and bOl'Ol'l trir t t o f0 t fluoride etherate were placed in a 3-neck round-bottom 1 Xazol one C fa 6p X1 6 r m n 1 flask. Epichlorohydrin (92.5 g.) (1 M) was added, con- (m. w. 732) o 2 I trolling the temperature at 80 C. The excess acid was Trlol 740 boron trlfluorlde etherate then neutralized by adding calcium oxide. To the mixture h l -)h Placed In a 3'neck round-bottom fiask- (1137 g.) was added dichloroethane (900 'rnl.), stannous Epic oro ydrin (370 g.) (41:4) Was lowly added, octoate catalyst (0.4 ml.) and tolylene dnsocyanate (2,4 trolling the temperature at 80 C. The excess catalyst was 2 19 01 111 Af condensanon was neutrallzed y Calclum OXlde; plete the reaction mixture was treated with sodium hyall? 1 1 $1.? 1333 311? id llifiifilitifii i i ii i 3325 (0303 t l il the i i f 5 to orm t e ioxazoi one e ra-epoxl e. and Stannous oqoate Catalyst Wlth Stlfrlng Cooled reaction and neutralized excess alkali with carbon f ii l y t l ft 5 -?0 -)C( d d, t l l dioxide. Filtered and removed solvent. This tetra-epoxide mg 6 @mPeTa We 6 Ween o an a OWlng had the following properties: temperature to climb to room temperature overnight. The mixture containing the poly(beta-haloalkylurethano) Aflalfilsi F011I1dC1, OXlrane, halohydrin was then treated with sodium hydroxide Viscosity: 2,400 P 31325 (105 g.) and the temperature controlled between 7080 C. to form the dioxazolidone tetra-epoxide. Cooled the EXAMPLE 21 reaction d lllltlaliled the BXCBSS li With CarbOn Dioxazolidone diepoxide-ep'oxy novolac resin composition gioixicllle. fillltered and removed solvent. This tetraepoxide cured ith nadi methyl anhydride a t e o 0w1n ro erties: Analysis, ig 2 Oxirane 2 7% 4 Epoxide equivalent weight of Dow epoxy novolac resin Viscosity; 1,876 at DEN 438:179. Viscosity of DEN 438 epoxy novolac Physical Properties: Blend'asin Example 11 resin: 19,000,000 cps. at 25 C. (approximate). The Cure 1 1 Week at 25 dioxazolidone diepoxide employed, referred to herein as DDP, was substantlally the same as that prepared in EX- ample 18(A). Oxirane found in DDP-3.40%epoxy Tenslle 400 equivalent weight: 471. Viscosity of DDP: 5100 cps. at Elmgatm, (percent) 66 25 C. Anhydride equivalent weight (molecular weight) 67 of Nadic methyl anhydride (NMA): 178.

i The following table shows various formulations, curing Tenslle 1000 conditions, and properties of resins produced from the g g g 82 above ingredients.

are

2 "r-'14542: t" tl ll'. 1 ."d d 0. e

*DEN 448 :179.

P Control Formulation Cure Tensile Percent Shore D Ki??? long. Hardness 7 days (1) DEN 438, 100 g. 24 hrs. at 90 0. plus 48 NMA, 89.5 hrs. at 125 0. 1,550 0.5 90 0.5 BDMA,10g (2) DDP, 30g o Dllqlali438, g g'isttllgfi cdplus48} 8,500 3.0 88 (l5 BDMA, 1 0 E1E 2411s tC 1 4s NMA, 62 g -j nr sfa t C us 84 M BDMA 1 (4) DDP, 66 g O satisfies-.1; 00st m 82 BDMA, 1.0

l 0.90 anhydride equivalent per epoxide equivalent. BDMA=Benzyldimethylamine.

O-OH,-CHCH2 CH:-CHCH2 0-CHr-CH-CH:

I 0 0 o OHFQ CHz n:1.6 (average) Procedure for making cured castings: The following coating vehicle solutions were made and The very viscous epoxy nov-olac resin was heated to 90 'Were coated on cleaned steel panels: C. in an oven to reduce its viscosity so that it could be poured. All of the ingredients of each formulation were [The amounts Ofthemgredlents are Parts by Weight] weighed into a 250 ml. 3-neck round-bottom flask. Each mixture was degassed by stirring and heating under vacuum Formulation No 1* 2 3 4 5 6 7* until the temperature of the mixture reached 85 C. (approxlmately 10 Inmates 0f Stlmng and 3)- Then Durez15959 phenolicresin 25.0 25.0 33 49 60 75 100 immediately the mixture was poured into a Vs" thick %l gg y e Teflon coated flat panel mold which had been preheated in J ggg; S in an oven to 90-100 C. The pouring was done carefully Solvent) 83 3 5 80 7 so as not to entrap air. The formulation was then cured Phosphoric acid 9 6% $01.

as shown above. The first 90 C. portion of the cure was tivn o 85% H3PO4 in n- 15 4 15 2 15 1 15 5 14 15 1 carried out in the mold. The solid casting was then removed from the mold before the second 125 C. stage of 67 67 67 63 71 71 45 the cure. 25 epoxy material) 41 as as 40 as 39 59.5

TABLE L-GHEMIOAL AND SOLVENT RESISTANCE OF DDP EPON 828 (2/1) Control.

Percent Change in Weight Chemicalor Solvent PENCIL HARDNESS DATA FOR THE CURED COATING 2 1 DDP/Epon 828 2/1 Epon 871 /Epon 828 2 20% sodium hydrox- 2 3 4 5 6 7* ide a 33 Toluene 47 55 Acetone 26 30 Weight ratio Durez Carbon tetrachloride- 30 89 phenolic resin/DD. 25/75 25/75 33/67 49/51 60/40 75/25 100/0 Hexane 0.1 9 Pencil hardness 1H 1H 1H 1H 1H 1H 4H Water 9 2 35 Epon 871 represents the standard-diglycidyl ester of dimer acid. *Gontrol Dimer acid is a 01s unsaturated fatty acid which has been dimen'zed #1 (hardr than coatings from formulations #2, 3 and containing at least one ethylenic double bond.

With aminoethylpiperazine curing agents, 7 days at room temperature (RT).

TABLE IL-BASIG FORMULA (211 DDP/EPON 828) [Curing agent in stoiehiometrle ratio, curing conditions: 73 F./50% relative humidity] AEP (Amino- Diethylene- Meta-xylene Bis- 1,4-eyclo- Curing Agent ethylpiperazine) triamine diamine Propanediamine (aminopropyl) hexane bispiperazine (methylamine) Tensile, 1 week *2, 550:1:0 (2, 2001200) 1, 850:l:50 2, 050:1:150 (1, 000:|=10. 0) 950x50 1,750;l;150 2,100;l;0 Percent elongation 14911.5 (73:l=6) 62 120. 55:1 (56. 5:1:2. 5) 845:3 92.5 80.8:l=1.3 Tenslitlle lcweek plus 48 hrs. 4, 400 4, 500:1:0 3, 7005:300 (2, 500:1:0) 3, 2005:100 3, 3001100 3, 700

a 5 Percent elongation 116 713:1.5 59. 5:l:8 (69.5:l:1) 72. 5+6 67.5=l:5.5 30 Shore hardness, 48 hrs. at

RT 50-33 (40-20) 40-27 50-33 (-34) 45-30 40-25 too soft Shore hardness, 1 week at RT 62-50 62-49 -35 (45-30) 50-35 58-45 -53 Capacitance:

*Figures in parentheses are the values for Epon 871 used as standard.

EXAMPLE 22 BENDING TEST nnsg r r s rgg COATINGS ON THE Diurethane diepoxide-phenolic resin coating vehicles N 65 [Panels were bent to elongate the coatings] The dlurethane diepoxide used in the following coat- Formulation A an 18 Comm Comm n t ing formulations was made from a 1.00/2107/24 molar No $5 5 cmke craclfedo ratio of Pluracol P-20-l0 (polypropylene glycol of 2000 molecular. weight) /TDI/bis[p,p'- (3-chloro-2-hydroxy-1- 332 oxypropyl)phenyl] isopropylidene. This diepoxide is re- 88:

ferred to in this example as DD. 0

0 I 0 I 250 X l w n Oxlrane found In dlurethane dlepoxlde (based on 7 Very brittle coating. Cracked du ing cooling ft of said material-mo solvent): 1.84%; total chlorine removal from curing oven. found: 16.2%; active chlorine found (hydrolyzable by NaHCO chlorohydrin chlorine): 0.68%. 75 The coating solutions were prepared by first dissolving 23 the DD or Epon 1007 solid epoxy resin in the Cellosolve acetate-toluene solvent combination with stirring. Heat was also required in the case of the Epon 1007 resin. Then the liquid Durez phenolic resin was added and dissolved by stirring. Last was added the phosphoric acid solution in butanol with continuous stirring.

Solvent-cleaned cold rolled SAE 1010 commercial grade flat steel panels, No. 20 gauge, 0.035 inch thick, satin finish, were used as the substrate for coatings of the above 7 formulations.

Each of the above 7 coating solutions was coated on 2 small steel panels by means of a Bird film applicator with a 0.006 gap to lay down wet films 0.006" thick. Then the coated panels were immediately laid horizontally in an oven at 145 C. and were cured at this temperature for 90 minutes. They were then removed from the oven and were allowed to cool, coated side up, at room temperature.

The bending tests were carried out by bending the panels so as to elongate the coatings. The panels were bent manually over the edge of a laboratory bench top to the approximate angles shown above for the various coating formulations. Theangles of bend are the angular deviations of the bent panels from the original flat shapes. Procedures for synthesis of the DD used in the above DD-phenolic resin coating vehicles Ingredients:

Pluracol P-201 (polypropylene glycol-2000 m.w.), 0.10 mole grams 200 TDI (tolylene diisocyanate), 0.207 mole grams 36.0 Stannous octoate catalyst (stabilized) ml 2.0 Bis[p,p-(3-chloro 2 hydroxy-l-oxypropyl) phenyl]isopropylidene, 0.24 mole grams 100 Ethylene dichloride sol-vent do 200 To a 2-liter-3-neck round-bottom flask were added the polypropylene glycol-2000, the ethylene dichloride solvent, the TDI, and half (1.0 ml.) of the stannous octoate catalyst. The flask had just been heated in an oven to remove traces of moisture and cooled to room temperature. The mixture was stirred for 4 hours. Then, the bis- [p,p'- 3-chloro-2-hydroxy- 1 -oxypropyl phenyl] isopropylidene was added as a 50% (by weight) solution in ethylene dichloride (200 gms. of solution) to the reaction mixture, and the other half (1.0 ml.) of the stannous octoate catalyst was then added. The solution was stirred for 1 hour.

After standing overnight, the reaction mixture and 60.0 gms. of 50% aqueous sodium hydroxide in 300 grams of ethylene dichloride solvent were put into a 2-liter flask previously heated to remove moisture. The contents of the flask were heated and stirred for 3 /2 hours, while the temperature was maintained at 75 :1" C. The mixture was then neutralized with CO dried over magnesium sulfate and filtered. Solvent was removed under vacuum until the measured solids content was 81.3%.

Analysis of product (based on 100% product-mo solvent): Oxirane oxygen found-1.84%;

Active chlorine found (hydrolyzable by NaHCO chlorohydrin chlorine)--0.68

EXAMPLE 23 Diurethane tetraepoxide made from triols formed by adding propylene oxide to trimethylol propane (1) Diurethane tetraepoxide from triol of 400 molecular weight (Pluracol TP 440 from Wyandotte Chemicals Corporation).

Diurethane tetraepoxide resin was prepared from a 1.00/2.00/ 6.60 molar ratio of TDI/triol/epicholorhydrin (EPCH).

Analysis of the diurethane tetraepoxide:

Oxirane oxygen found-3.54%. Total chlorine found-3.62%. Viscosity of resin29,200 centipoises at 25 C.

Cure Tens. Elong. Shore D Diurethane tetra- 1 wk. at RT 350 49 19 epoxide, 100 g. AEP, 9.4 g 1 wk. at 105 C... 750 77 22 Diurethane tetra- 66 g.

epoxide resin, 66g. Diglycidyl ether of 1 wk. at RT.-. 3, 750 8 65 bisphenol A (Epon 828 epoxy 33 1 k t105 o 7 400 4 74 w a AEP'Z g wk. at 105 8,250 6 75 1 Room temperature. 2 Stoichiometric quantity of AEP (aminoethylpiperazine).

(2) Diurethane tetraepoxide made from triol of 700 molecular weight (Pluracol TP 740 from Wyandotte Chemicals Corporation) Diurethane tetraepoxide resin was prepared from a 1.00/ 2.29/ 6. molar ratio of TDI/triol/EPCH.

Analysis of the diurethane tetraepoxide:

Oxirane oxygen found2.43 Total chlorine found-2.54% Active chlorine found (chlorine hydrolyzable by NaHCO )-0.84% Viscosity at 25 C.4,650 centipoises Cure Tens. Elong. Shore D Diurethane tetra- 1 Wk. at RT 80 21 2 55 epoxide, g. AEP) 6.5 g 1 w. at 80 26 2 57 Diurethane tetra- 1 wk. at RT 3, 600 30 07 epoxide, 50 g. Diglycidyl ether of 1 wk. at 105 4, 200 28 J1 bispncnol A (Epon 828 epoxy resin), 50 g. AEP, 14.5 g

1 Room temperature. 2 Shore A. 3 Stoichiometric quantity of AEP.

Diurethane tetraepoxide was prepared from a 1.00/ 2.22/ 6.67 molar ratio of TDI/triol/EPCH 5 Analysis of the diurethane tetraepoxide:

Oxirane oxygen found2.84% Total chlorine found-4.71% Viscosity of 25 C.84 centipoises Cure Tens. Elong. Shore D Diurethane tetra- 1 wk. at RT 1,200 72 28 epoxide, 66 g. Diglycidyl ether of 1 wk. at RT 1, 440 74 35 bis-phenol A plus 1 wk. at

(Epon 828 epoxy 105 C.

resin), 33 g. AEP, 12.5 g do 1, 800 85 36 1 Room temperature. 2 Stoichiometrie quantity of AEP.

Procedure for synthesis of the diurethane tetraepoxide used in the last formulation above:

6 Trial 740 trimethylolpropanepropylene oxide condensates of approximately 7 00 molecular weight.

Procedure The triol was weighed into 3-liter, 3-neck flask equipped with a glass stirrer, thermometer, addition funnel, and reflux condenser. Next, the BF etherate was added. The mixture was heated to 70 C., and the epichlorohydrin was added dropwise while the temperature of the reaction mixture was maintained at 70 C. with an ice bath. The addition of the epichlorohydrin required 40 minutes. The

reaction mixture was stirred at 70 C. for 1 hour after the addition of epichlorohydrin was completed. The re action mixture was cooled to C. and diluted with 500 ml. of ethylene dichloride solvent. The TDI was then added dropwise while the temperature of the reaction mixture was maintaied at 10 C. during the addition and for 2 hours of stirring after the addition was completed. The reaction mixture was allowed to stand at room temperature overnight.

The sodium hydroxide was added quickly while the temperature of the reaction mixture was maintained .at 80 C. with stirring, and stirring was continued at 80 C. for a total of 2 hours after the start of the addition of the sodium hydroxide.

The reaction mixture was then neutralized with CO dried over Na SO for 30 minutes, and filtered.

The solvent was removed by heating with a steam bath under vacuum.

Yield of product-851 grams Theoretical yield995 .5 grams Percent yield-85 .5

Analysis of diurethane tetraepoxide product:

Oxirane found-2.84% Total chlorine found-2.7 Viscosity at 25 C.--8400 centipoises EXAMPLE 24 Ethyl isocyanate (0.1mole, 7.1 g.) was mixed with isopropylidene bis[1 (p-phenyleneoxy) 3-chloro-2-propa- 1101] (41.5 g., 0.1 mole), 42 g. ethylene dichloride and 0.5 ml. stannous octoate. The mixture was allowed to stand overnight at room temperature to form the (betachloroalkylurethano) chlorohydrin. The mixture was then diluted with 150 ml. ethylene dichloride. At 70-75 C., over a period of 30 minutes, 16 g. (0.4 mole) of sodium hydroxide flakes was added portion-wise with stirring. Stirring was continued for an additional hour period. The reaction mixture was cooled, neutralized with carbon dioxide and filtered. Upon concentration to dryness in vacuo the epoxy oxazolidinone was obtained in the form of a viscous, yellow syrup. Upon polymerization with boron trifluoride etherate, a solid resin was recovered.

EXAMPLE 25 Isopropyl isocyanate (0.1 mole, 8.5 g.) was mixed with 115.0 g. (0.1 mole) of polyepichlorohydrin 1150 (a dichlorohydrin from the Dow Chemical Co.), 120 ml. of ethylene dichloride and 0.5 ml. stannous octoate. The mixture was allowed to stand overnight at room temperature to form the (beta-chloroalkylurethano) chlorohydrin. This was then diluted with 110 ml. of ethylene dichloride. At 70-75" C., 16 g. (0.4 mole) of sodium hydroxide flakes was added as in Example 8. By continuing the procedure of Example 24, a viscous syrupy product was obtained. The epoxy oxazolidinone product was polymerized with boron trifluoride etherate and a solid resin was recovered.

EXAMPLE 26 Dodecyl isocyanate (0.1 mole, 21.1 g.) was mixed with isopropylidene bis[1 (p phenyleneoxy)-3-chloro-2-propanol] (41.5 g., 0.1 mole), 75 g. ethylene dichloride and 0.5 ml. stannous octoate. The mixture was allowed to stand overnight at room temperature to form the (betachloroalkyluret-hano) chlorohydrin. The mixture was then diluted with 150 ml. ethylene dichloride. At 7075 C., over a period of 30 minutes, 16 g. (0.4 mole) of sodium hydroxide flakes was added portion-wise with stirring. By continuing the procedure, as in Example 24, a viscous syrupy product was obtained. The epoxy oxazolidinone product was polymerized with boron trifluoride etherate and a solid resin was recovered.

EXAMPLE 27 a-Naphthyl isocyanate (0.1 mole, 16.9 g.) was mixed with 1,4-di(3-chloro-2-ol-propyloxy)butane (27.5 g., 0.1. mole), 40 ml. of ethylene dichloride and 0.5 ml. stannous octoate. The mixture was allowed to stand overnight at room temperature to form the (beta-chloroalkylurethano) chlorohydrin. It was then diluted with 110 ml. of ethylene dichloride. At 70-75 C., 16 g. (0.4 mole) of sodium hydroxide flakes was added as in Example 24. By continuing the procedure of Example 24 a viscous amber syrup was obtained. Again a solid resin was recovered after polymerization of the epoxy oxazolidinone product with boron trifluoride.

EXAMPLE 28 A monoisocyanate was prepared by treating 17.4 g. (0.1 mole) of toly lene diisocyanate (80% 2,4; 20% 2,6) with 13.0 g. (0.1 mole) of 1-octanol in 100 ml. ethylene dichloride in the presence of 0.2 ml. stannous octoate for 4 hours at room temperature, then at 3 hours at 40 C. Isopropylidene (bis[1 (p-phenyleneoxy)-3-chloro-2-propanol] (41.5 g., 0.1 mole) and 0.4 m1. stannous octoate were added; the mixture was then allowed to stand overnight at room temperature to form the (beta-chloroalkylurethano) ha lohydrin. At 70-75" C., 16 g. (0.4 mole) of sodium hydroxide flakes was added as in Example 24. By following the procedure of Example 24 a viscous syrupy product was obtained. Again, a solid resin was recovered after polymerization of the epoxy oxazolidinone product with boron trifluoride.

In the preceding examples, tensile strength was measured in accordance with ASTM 638-52TD and recovered as pounds per square inch (p.s.i.), whereas the tests on electrical properties were measured in accordance with ASTM D-150-59T and ASTM D-150-54T.

As stated hereinbefore, the novel compounds of this invention include those prepared from a monoisocyanate (instead of a polyisocyanate) and a dihalohydrin. Also, other poly(halohydrins) can be employed in place of a di(halohydrin) in the reaction with a monoisocyanate. The poly(halohydrins) mentioned hereinbefore can be employed in preparing such compounds, but preferably the halohydrin groups of the polyhalohydrins are separated by at least one carbon atom. The monoisocyan-ate reactant can be of the types mentioned hereinbefore for polyisocyanates, e.g., a compound of the formula wherein x is 1 and R is a monovalent aromatic or aliphatic group, e.g., alkyl, aryl, etc. These epoxyoxazolidinones can be represented by the formula:

wherein Z is selected from aliphatic and aromatic structures consisting of alkyl, substituted alkyl, alkyloxy, al-

kenyl, substituted alkenyl, aryl and substituted aryl; Z is selected from aliphatic and aromatic structures consisting of alkylene, substituted alkylene, alkyleneoxy, cycloalkylene, substituted cycloalkylene, arylene, substituted arylene, aralkylene and substituted aralkylene; and m is an integer from 1 to 5. Preferably, Z is hydrocarbyl having from about 6 to about 12 carbon atoms, e.g., alkyl, alkphenyl, and the like; m is 1 and Z represents preferred Z groups for the epoxyoxazolidinones as set forth in Formula B.

In preparing preferred compositions of this invention, the epoxyoxazolidinone compounds have the structure shown in Formula B, wherein Z is attached to the 5 carbon atom of the oxazolidinone ring. However, isomeric compounds are coproduced wherein Z is attached to the 4 carbon atom of the oxazolidinone ring as shown in For- 27 mula C. Such isomeric compounds are illustrated by the formula:

-or-r, ZN-CH- '-CI-I-CH wherein Z, Z, m and n have the same meaning as in Formula B.

What is claimed is:

1. A polymerizable composition comprising: (A) a substituted 2-oxazolidinone of the formula ZNo L .1.

wherein Z is the organic residue of hexamethylene diisocyanate, xylylene diisocyanate, 1-methyl-2,4-diisocyanatohexane, phenylene diisocyanate, tolylene diisocyanate, 'chlorophenylene diisocyanate, diphenylmethane-4,4- diisocyanate, naphthalene 1,5-diisocyanate, or triphenylmethane-4,4',4"-triisocyanate; Z is the organic residue of a poly(chlorohydrin), said poly(chlorohydrin) selected from the group consisting of isopropylidene bis[l-(phenyleneoxy) 3-chloro-2-propanol], 3,3'-dichloro-2,2'-dihydroxydipropylether, poly(epichlorohydrin), the epichlorohydrin adduct of (a) poly (oxyalkylene) glycol having from 2 to 4 carbon atoms in each alkylene group, (b) resorcinol, (c) glycerol, ((1) pentaerythritol, (e) sorbitol, (f) hexane 1,6-diol, and (g) trimethylol propane, said Z attached to the 4 or carbon atom of the oxazolidinone ring and the remaining valence of said 4 or 5 carbon atom satisfied with a hydrogen atom; in is an integer of 1 to 5 and n is an integer of 2 to 10, wherein said epoxyoxazolidinone has a molecular weight of not greater than about 5,000; and (B) a polymerization catalyst in a quantity of from about 0.005 to 15% by weight of polymerizable material in said composition.

2. Polymers produced by heating the polymerizable composition of claim 1.

3. A polymerizable composition comprising: (A) a substituted 2-oxazolidinone of the formula wherein Z is the organic residue of hexamethylene diisocyanate, xylylene diisocyanate, 1-rnethyl-2,4-diisocyanatohexane, phenylene diisocyanate, tolylene diisocyanate, chlorophenylene diisocyanate, diphenylmethane-4,4-diisocyanate, naphthalene, 1,5-diisocyanate, or triphenylmethane-4,4,4-triisocyanate; Z is the organic residue of a po1y(chlorohydrin), said poly(chlorohydrin) selected from the group consisting of isopropylidene bis[l-(phenyleneoxy) -3-chloro-2-propanol] 3,3-diehloro-2,2'-dihydroxydipropylether, poly(epichlorohydrin), the epichlorohydrin adduct of (a) poly(oxyalkylene) glycol having from 2 to 4 carbon atoms in each alkylene group, (b) resorcinol, (c) glycerol, (d) pent-aerythritol, (e) sorbitol, (f) hexane 1,6-diol, and (g) trimethylol propane, said Z attached to the 4 or 5 carbon atom of the oxazolidinone ring and the remaining valence of said 4 or 5 carbon atom satisfied with a hydrogen atom; m is an integer of 1 to 5 and n is an integer of 2 to 10, wherein said epoxyoxazolidinone has a molecular weight of not greater than about 5,000 and (b) an epoxy reactive comonomer, said epoxy reactive comonomer comprising, (a) a polyol in a quantity sufiicient to provide between about 0.2 to 4.0 hydroxyl equivalents per epoxy equivalent of said oxazolidinone, (b) a polyfunctional amine having at least two active amino hydrogen atoms in an amount sufficient to provide between about 0.2 to 4.0 amino hydrogen atoms per epoxy equivalent of said oxazolidinone, (c) a polycarboxylie acid in an amount sufficient to provide between 0.3 and 3.0 carboxyl equivalents per epoxy equivalent of said epoxyoxazolidinone, (d) a polycarboxylic acid anhydride in a quantity sutficient to provide between 0.2 to 4.0 carboxyl equivalents of anhydride per epoxy equivalent of said oxazolidinone, (e) a polyepoxide, other than that of said oxazolidinones, in an amount sufficient to provide between 0.2 to 4.0 epoxy equivalents per epoxy equivalent of said oxazolidinone.

4. Copolymers produced by heating a polymerizable composition of claim 3.

5. A polymerizable composition comprising: (a) a substituted 2-oxazolidinone of the formula:

II o wherein Z is tolylene, R is propylene, and n represents repeating units of the (OR) group and b an epoxy reactive comonomer.

6. A polymeric composition comprising the reaction product of: (a) a poly(epoxyoxazolidinone) of the formula:

wherein Z is the divalent organic residue of a dichlorohydrin, said dichlorohydrin selected from the group consisting of isopropylidene bis[l-(phenyleneoxy)-3-chlorol-propanol] 3 ,3'-dichloro-2,2'-dihydroxydipropylether, poly(epichlorohydrin), the epichlorohydrin adduct of (a) poly (oxyalkylene) glycol having from 2 to 4 carbon atoms in each alkylene group, and (b) hexane 1,6-diol; wherein Z is a divalent hydrocarbon group having from about 6 to 12 carbon atoms selected from the group consisting of alkylene, alkphenylene and phenylene; m is 1; n is 2; and wherein said compound has a molecular weight of not greater than 5,000; (b) a polyglycidyl ether of a polyhydric phenol; and (c) a cross linking curing agent for the epoxy groups, the said polymer containing the reaction product in a ratio of 1 to 10 and 10 to 1 parts by weight of the said oxazolidinone to the polyglycidyl ether of a polyhydric phenol and ((1) wherein the quantity of said curing agent is sufficient to provide from 0.5 to 2 epoxy reactive sites for each epoxy group of the oxazolidinone and phenolic polyepoxides.

7. A polymeric composition of claim 6 wherein (a) the poly(epoxyoxazolidinone) is of the formula wherein Z is tolylene, R is propylene, n represents repeating units of said (OR) group, said units being equal to the number of such groups in polypropylene glycol having a molecular weight of from about to 1,000; (b) wherein the polyglycidyl ether of the polyhydric phenol is 'a member selected from the group consisting of an epoxylated novolac resin and a diglycidyl ether epichlorohydrin adduct of bis(4-hydroxyphenyl) dimethylmethane; wherein the curing agent is a polyfunctional amine having at least two active amino hydrogen atoms, and wherein the polymeric composition contains from about 0.2 to 5 parts by weight of the oxazolidinone compound for each part of the polyglycidyl ether of the polyhydric phenol.

8. A composition of claim 7 wherein the curing agent is aminoethylpiperazine.

9. A po'lymerizable composition of claim 3 wherein the epoxy reactive comonomer is a polyfunctional amine.

10. A copolymer produced by heating the polymerizable composition of claim 9.

30 References Cited UNITED STATES PATENTS 3/ 1957 Schul-ler 260-307.3 11/1958 Newcomer 260-3073 12/1960 Arend 260-307.3

3/ 1961 Oken 260-307.3

2/ 1962 Speranza 260-3073 MURRAY TILLMAN, Primary Examiner.

10 PAUL LIEBERMAN, Assistant Examiner.

US. Cl. X.R.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,415 ,901 December 10 1968 Charles H. Schramm et al.

It is certified that error appears in the above identified patent and that said Letters Patent are hereby corrected as shown below:

Column 4 line 21 "orgaic" should read organic line 69, "phenylphosphoric" should read phenylphosphonic lines 72 and 73, "=SiR(SO NCO) and the like." should read sSi-NCG group, isocyanates derived from sulfonamides, (R(SO NCO) and the like Column 6 line 49 "epoxyclohexyl" should read epoxycyclohexylline 56, "or" should read of Column 7 line 72 "zinc fluorborate" should read zinc fluoborate Column 8 line 74 "etdylenediamine" should read ethylenediamine Column 10 line 12 "modified" should read modifier Column 13 line 12 "curer" should read cured in the table heading to the second column, line 2 thereof, "gsm. should read gms line 73 "ot" should read to Column 14 line 58 "metal and Thermit" should read Metal and Thermit line 67 "azeotrope" should read azeotropic Column 17 line 50 "diop" should read diepline 56 "clycol" should read glycol Column 18 line 5, "di (B-chloromethylurethona) should read di [B-chloromethylurethano] Column 20 line 59 in footnote 4 448 179" should read 438 179 Columns 19 and 20 in the table heading to the last column, line 1 thereof, after "Percent" insert Water Columns 21 and 22 lines 1 to 9 extreme right-hand portion of the formula reading "CH should read CH Column 21 line 75 "NaHCO should read NaHCO Columns 21 and 22 TABLE II second column, line 13 thereof, "1 4+lO should read l .4 1D same table fourth column, line 1 thereof,

"10.0" should read 100 Column 22 in the first table eighth column, line 7 thereof, "59 5" should read 49 5 same column 22 heading to the second table "COATING" should read COATINGS same second table seventh and eighth columns line 2 thereof, 1H" and 4H" should read 1H and 4H Column 23, line 59 "NaHCO should read NaHCO Column 24 in the first table second column, line 3 thereof, cancel "66 g. line 42 "of" should read at line 58 "BF should read BF line 62 "2 .4" should read 2 ,4 same line 62 "2 .6" should read 2 ,6 line 71 "BF should read BF same column 24 at the bottom of the column, insert as a footnote Epichlorohydrin Column 25 line 16 "Na SO should read Na SO Column 28 lines 20 to 26 before the opening bracket of the formula, insert Signed and sealed this 16th day of June 1970.

(SEAL) Attest:

EDWARD M. FLETCHER,JR. WILLIAM E. SCHUYLER, JR. Attesting Officer Commissioner of Patents 

